JPH0613672B2 - Modified maleimide resin varnish - Google Patents
Modified maleimide resin varnishInfo
- Publication number
- JPH0613672B2 JPH0613672B2 JP62182264A JP18226487A JPH0613672B2 JP H0613672 B2 JPH0613672 B2 JP H0613672B2 JP 62182264 A JP62182264 A JP 62182264A JP 18226487 A JP18226487 A JP 18226487A JP H0613672 B2 JPH0613672 B2 JP H0613672B2
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide
- solvent
- maleimide resin
- resin
- resin varnish
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 23
- 239000011347 resin Substances 0.000 title claims description 23
- 239000002966 varnish Substances 0.000 title claims description 15
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 title 1
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 23
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 12
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 150000004292 cyclic ethers Chemical group 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- -1 1,2- Epoxyethyl Chemical group 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- BTFWJAUZPQUVNZ-UHFFFAOYSA-N 1-methyl-3-[(3-methylphenyl)methyl]benzene Chemical compound CC1=CC=CC(CC=2C=C(C)C=CC=2)=C1 BTFWJAUZPQUVNZ-UHFFFAOYSA-N 0.000 description 1
- BPHYZRNTQNPLFI-UHFFFAOYSA-N 2,4,6-trihydroxytoluene Chemical compound CC1=C(O)C=C(O)C=C1O BPHYZRNTQNPLFI-UHFFFAOYSA-N 0.000 description 1
- NZHNJOJQMPJLFA-UHFFFAOYSA-N 2-[3,5-bis(oxiran-2-yl)phenyl]oxirane Chemical compound C1OC1C1=CC(C2OC2)=CC(C2OC2)=C1 NZHNJOJQMPJLFA-UHFFFAOYSA-N 0.000 description 1
- IHMXVSZXHFTOFN-UHFFFAOYSA-N 2-ethyloxolane Chemical compound CCC1CCCO1 IHMXVSZXHFTOFN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- HVMHLMJYHBAOPL-UHFFFAOYSA-N 4-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propan-2-yl]-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1C(C)(C)C1CC2OC2CC1 HVMHLMJYHBAOPL-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は作業性、硬化性が良好で接着性が、ドリル加工
性、寸法安定性に優れた耐熱性の変性マレイミド樹脂ワ
ニスに関するものである。TECHNICAL FIELD The present invention relates to a heat-resistant modified maleimide resin varnish having excellent workability, curability, adhesiveness, drill workability, and dimensional stability. .
従来、熱硬化性耐熱樹脂としてビスマレイミド、ポリア
ミノビスマレイミド樹脂などがよく知られている。ビス
マレイミドは、溶解性、硬化性が悪く、十分に硬化させ
たものは耐熱性に優れているが脆く、接着性も弱く、実
用性に欠けているために芳香族ジアミンで変性しポリア
ミノビスマレイミド樹脂として実用化されている。しか
しながら、このポリアミノビスマレイミド樹脂は高沸点
の極性溶媒にしか溶けず、又硬化速度が遅いために成形
温度を高くしたりポストキュアーに多大の工数をかけな
ればならず、又脆さと接着性については十分に改良され
てはいない。Conventionally, bismaleimide, polyamino bismaleimide resin, and the like are well known as thermosetting heat-resistant resins. Bismaleimide is poor in solubility and curability, and when fully cured, it has excellent heat resistance but is fragile, has poor adhesiveness, and lacks practicality. Therefore, it is modified with an aromatic diamine to give a polyamino bismaleimide. It has been put to practical use as a resin. However, this polyamino bismaleimide resin is only soluble in polar solvents with a high boiling point, and since the curing rate is slow, it is necessary to raise the molding temperature and to spend a lot of time for post cure, and also regarding brittleness and adhesiveness. Is not fully improved.
本発明は、ビスマレイミドと適度の分子量分布を有する
マレイミドのオリゴマーを配してなるマレイミド樹脂は
融点が低く、又低沸点溶媒に対して溶解性が良好である
との知見を得、さらに研究を進めた結果、該マレイミド
樹脂にエポキシ樹脂及びフェノール樹脂を配することに
より、硬化性が良好で、接着性、ドリル加工性、寸法安
定性に優れ、更に作業性が良好な変性マレイミド樹脂ワ
ニスを提供するにある。The present invention, bismaleimide and maleimide resin obtained by arranging an oligomer of maleimide having an appropriate molecular weight distribution has a low melting point, also obtained the knowledge that the solubility in a low boiling point solvent is good, further research As a result, by providing an epoxy resin and a phenolic resin in the maleimide resin, a modified maleimide resin varnish having good curability, excellent adhesiveness, drilling workability, dimensional stability, and good workability is provided. There is.
本発明は、無水マレイン酸と芳香族ジアミンとの反応か
ら得られるビスマレイミドを４０〜７０重量％及び分子
量５００〜５０００のプレポリマーを６０〜３０重量％
含有するマレイミド樹脂(A)、エポキシ樹脂(B)、及びフ
ェノール樹脂(C)を必須成分とし、該組成比が(B)／(A)
が０．１〜２であり、(C)／(A)が０．０５〜０．５であ
る組成物を溶剤に溶かしてなる変性マレイミド樹脂ワニ
スに関するものである。The present invention comprises 40 to 70% by weight of a bismaleimide obtained from the reaction of maleic anhydride and an aromatic diamine and 60 to 30% by weight of a prepolymer having a molecular weight of 500 to 5000.
Maleimide resin (A), epoxy resin (B), and phenol resin (C) contained are essential components, and the composition ratio is (B) / (A)
Of 0.1 to 2 and (C) / (A) of 0.05 to 0.5 are dissolved in a solvent to provide a modified maleimide resin varnish.
本発明のマレイミド樹脂の成分の１つであるビスマレイ
ミドは、下記の式(1)で表される。Bismaleimide, which is one of the components of the maleimide resin of the present invention, is represented by the following formula (1).
（Ｒは、２価の芳香族基を表す。） 具体例としては、N,N′−ｍ−フェニレンビスマレイミ
ド、N,N′−ｐ−フェニレンビスマレイミド、N,N′−ｍ
−トルイレンビスマレイミド、N,N′−4,4′−ビフェニ
レンビスマレイミド、N,N′−4,4′−〔3,3′−ジメチ
ル−ビスフェニレン〕ビスマレイミド、N,N′−4,4′−
ジフェニルメタンビスマレイミド、N,N′−4,4′−〔3,
3′−ジメチルジフェニルメタン〕ビスマレイミド、N,
N′−4,4′−〔3,3′−ジエチルジフェニルメタン〕ビ
スマレイミド、N,N′−4,4′−ジフェニルプロバンビス
マレイミド、N,N′−4,4′−ジフェニルエーテルビスマ
レイミド、N,N′−3,3′−ジフェニルスルホンビスマレ
イミド、N,N′−4,4′−ジフェニルスルホンビスマレイ
ミドなどをあげることができる。これらは、２種以上含
まれていても何ら支障はない。 (R represents a divalent aromatic group.) Specific examples include N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m.
-Toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 '-[3,3'-dimethyl-bisphenylene] bismaleimide, N, N'-4 , 4′−
Diphenylmethane bismaleimide, N, N'-4,4 '-[3,
3'-Dimethyldiphenylmethane] bismaleimide, N,
N'-4,4 '-[3,3'-diethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenylprobanbismaleimide, N, N'-4,4'-diphenylether bismaleimide, N , N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, and the like. There is no problem even if two or more of these are contained.
ビスマレイミドは、マレイミド樹脂中に、４０〜７０重
量％含まれることが必要である。これより多い場合は、
溶剤に対する溶解性が低下し、沈澱を生じて、ワニスの
保存性を極度に悪化させる。また、硬化速度も遅い。一
方、少な過ぎる場合は、分子量の大きい成分が増大する
こととなり、このうち一部に分子量10,000以上の高分子
量成分も含まれてしまい、不溶物が生じたり、ワニス粘
度が極度に増大したり、粘度増加によって、ワニスの可
使時間が非常に短くなるなどの不都合が生ずる。The bismaleimide needs to be contained in the maleimide resin in an amount of 40 to 70% by weight. If more than this,
Solubility in a solvent is lowered, and precipitation occurs, which extremely deteriorates the storage stability of the varnish. Also, the curing speed is slow. On the other hand, when the amount is too small, the component having a large molecular weight is increased, and a high molecular weight component having a molecular weight of 10,000 or more is also included in a part thereof, insoluble matter is generated, or the varnish viscosity is extremely increased, The increase in viscosity causes disadvantages such as a very short pot life of the varnish.
マレイミド樹脂中の分子量５００以上、5000以下の成分
は、過剰の無水マレイン酸と芳香族ジアミンとを、無溶
媒下、１３０〜２００℃の温度で反応させた時、分子内
の脱水縮合反応によって得られるビスマレイミドと同時
に生成するプレポリマーで、主として、分子間の脱水縮
合反応によって得られるものである。The component having a molecular weight of 500 or more and 5000 or less in the maleimide resin is obtained by an intramolecular dehydration condensation reaction when an excess amount of maleic anhydride and an aromatic diamine are reacted at a temperature of 130 to 200 ° C. in the absence of a solvent. It is a prepolymer formed at the same time as the bismaleimide, and is mainly obtained by an intermolecular dehydration condensation reaction.
分子量５００以上、５０００以下の成分は、ビスマレイ
ミドの融点を下げ、溶剤に対する溶解性を助長し、高価
な項沸点の極性溶媒だけでなく、テトラヒドロフラン、
ジオキサンなどの環状エーテル類にも容易に溶けるよう
になる。A component having a molecular weight of 500 or more and 5000 or less lowers the melting point of bismaleimide, promotes solubility in a solvent, and not only an expensive polar solvent having a boiling point, but also tetrahydrofuran,
It becomes easily soluble in cyclic ethers such as dioxane.
分子量が５０００より大きい成分は、環状エーテル類に
対する溶解性が低下してしまい同じ樹脂含有率でのワニ
ス粘度が高く、しかも増粘速度が速く、ワニスの可使時
間が非常に短くなってしまう。If the component has a molecular weight of more than 5,000, the solubility in cyclic ethers is lowered, the viscosity of the varnish at the same resin content is high, the viscosity increasing rate is high, and the pot life of the varnish is very short.
分子量５００以上、５０００以下の成分は、樹脂中に３
０〜６０％含まれていることが好ましい。３０％未満で
は、ビスマレイミドが多過ぎるため、溶解性が低下し、
沈澱を生じて、ワニスの保存性が悪化する。一方、６０
％より多いと、分子量が5,000より大きい成分も含まれ
てしまい、前述の不都合を生ずる。ここで、分子量は、
テトラヒドロフランを溶媒とし、東洋曹達(株)製ＴＳＫ
−ＧＥＬ−Ｇ−１００Ｈ（１本）、Ｇ−２０００Ｈ（２
−本）、Ｇ−３０００Ｈ（１本）を装置したゲル浸透ク
ロマトグラフ（ＧＰＣ）で測定し、標準ポリスチレン検
量線による換算した値である。Components with a molecular weight of 500 or more and 5000 or less
It is preferable that the content is 0 to 60%. If it is less than 30%, the amount of bismaleimide is too much, so that the solubility decreases,
Precipitation occurs and the storage stability of the varnish deteriorates. On the other hand, 60
If it is more than%, a component having a molecular weight of more than 5,000 is also contained, which causes the above-mentioned inconvenience. Here, the molecular weight is
Tetrahydrofuran as a solvent, TSK manufactured by Toyo Soda Co., Ltd.
-GEL-G-100H (1), G-2000H (2
-This) and G-3000H (1) were measured by a gel permeation chromatograph (GPC), and the values were converted by a standard polystyrene calibration curve.
エポキシ樹脂としては、特に制約は無いが、例えばビス
フェノールＡのジグリシジエーテル、4,4′−ジ（1,2−
エポキシエチル）ジフェニルエーテル、4,4′−（1,2−
エポキシエチル）ジフェニルエーテル、レゾルシンのジ
グリシジルエーテル、ブタジエンジエポキシサイド、ビ
ス−（2,3−エポキシシクロペンチル）エーテル、2,2−
ビス（3,4−エポキシシクロヘキシル）プロパン、フロ
ログルシンのジグリシジルエーテル、メチルフロログル
シンのジグリシジルエーテルなどの２官能のエポキシ化
合物フェノール類−ホルムアルデヒドノボラックのポリ
グリシジルエーテル、トリメチロールプロパンのトリグ
リシジルエーテル、グリセリンのトリグリジシルエーテ
ル、1,3,5−トリ（1,2−エポキシエチル）ベンゼン、ポ
リアクリルグリシジルエーテル、パラアミノフェノール
のトリグリシジルエーテルなどの３官能以上のエポキシ
化合物が用いられる。これらの化合物は、用途、目的に
応じて単独もしくは併用して使用することができる。エ
ポキシ樹脂の添加量はマレイミド樹脂１００重量部に対
し、１０〜２００重量部が好ましい。The epoxy resin is not particularly limited, but for example, diglycidyl ether of bisphenol A, 4,4'-di (1,2-
Epoxyethyl) diphenyl ether, 4,4 '-(1,2-
Epoxyethyl) diphenyl ether, diglycidyl ether of resorcin, butadiene diepoxy side, bis- (2,3-epoxycyclopentyl) ether, 2,2-
Bifunctional epoxy compounds such as bis (3,4-epoxycyclohexyl) propane, diglycidyl ether of phloroglucin, diglycidyl ether of methyl phloroglucin, phenols-polyglycidyl ether of formaldehyde novolac, triglycidyl ether of trimethylolpropane, Trifunctional or higher functional epoxy compounds such as triglycidyl ether of glycerin, 1,3,5-tri (1,2-epoxyethyl) benzene, polyacrylglycidyl ether, and triglycidyl ether of paraaminophenol are used. These compounds can be used alone or in combination depending on the application and purpose. The amount of the epoxy resin added is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the maleimide resin.
エポキシ樹脂が少な過ぎると、接着性、ドリル加工性の
向上が十分でなく、多過ぎるとガラス転移温度などの耐
熱性が低下する。If the amount of the epoxy resin is too small, the adhesiveness and drill workability are not sufficiently improved, and if it is too large, the heat resistance such as the glass transition temperature decreases.
フェノール樹脂は、通常のノボラック型フェノール樹脂
又は固型のレゾール型フェノール樹脂が使用される。フ
ェノール樹脂は添加量は、マレイミド樹脂１００重量部
に対し、５〜５０重量部が好ましい。フェノールが少な
過ぎるとエポキシ樹脂と同様に接着性、ドリル加工性の
向上が十分でなく、寸法安定性を劣り、多過ぎるとガラ
ス転移温度などの耐熱性が低下する。As the phenol resin, a normal novolac type phenol resin or a solid type resol type phenol resin is used. The addition amount of the phenol resin is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the maleimide resin. When the amount of phenol is too small, the adhesiveness and drilling processability are not sufficiently improved like the epoxy resin, and the dimensional stability is poor, and when it is too large, the heat resistance such as the glass transition temperature is lowered.
本発明で用いる溶剤は、ジメチルホルムアミド、ジメチ
ルアセトアミド、N-メチルピロリドンなどの高沸点極性
溶剤も使用できるが、低温、短時間で溶剤の除去が可能
な作業性の良い低沸点の環状エーテル類がより好まし
い。As the solvent used in the present invention, dimethylformamide, dimethylacetamide, and high boiling point polar solvents such as N-methylpyrrolidone can also be used, but low-temperature, low-boiling cyclic ethers with good workability that can remove the solvent in a short time are More preferable.
環状エーテル類としてはテトラヒドロフラン、２−メチ
ルテトラヒドロフラン、３−メチルテトラヒドロフラ
ン、2,5−ジメチルテトラヒドロフラン、２−エチルテ
トラヒドロフラン、1,4−ジオキサン、1,3−ジオキサン
などをあげることができる。また、これらを主溶剤とし
て、溶解性を悪化させない範囲で、他の一般有機溶剤を
添加した混合溶剤であってもかまわない。Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2-ethyltetrahydrofuran, 1,4-dioxane and 1,3-dioxane. A mixed solvent containing these as a main solvent and other general organic solvent may be added as long as the solubility is not deteriorated.
変性マレイミド樹脂ワニスには、必要に応じて、第３級
アミン類、イミダゾール類、ホスフィン類あるいは有機
過酸化物などの硬化触媒が配合される。If necessary, the modified maleimide resin varnish is mixed with a curing catalyst such as a tertiary amine, an imidazole, a phosphine or an organic peroxide.
本発明による変性マレイミド樹脂ワニスは、低沸点溶剤
が使用できるため、作業性にすぐれ、硬化触媒等の使用
も容易にできる。このため硬化性が良好で低温で硬化が
可能であり、更に得られた硬化物は耐熱性、接着性、ド
リル加工性、寸法安定性、などに優れており、積層板、
多曹プリント板などの製造において非常に優れたワニス
である。Since the modified maleimide resin varnish according to the present invention can use a solvent having a low boiling point, it has excellent workability and can easily be used as a curing catalyst or the like. Therefore, it has good curability and can be cured at low temperatures, and the resulting cured product has excellent heat resistance, adhesiveness, drilling workability, dimensional stability, etc.
It is a very excellent varnish in the production of polysodium printed boards.
［マレイミド樹脂の合成例］ 合成例１〜５ 第１表の配合に従って、無水マレイン酸を融解し、これ
に芳香族ジアミンを徐々に添加し、添加後、３００〜１
００mmHgの減圧下で、第１表の条件により脱水反応させ
た。反応後、キシレン２０ｇと熱水２００ｇとを加え、
還流させながら、５分間、撹拌混合した。静置すると、
抽出水が上層に分離する。これを吸引除去し、更に熱水
２００ｇを２回加え、同様に、洗浄をくり返した。その
後、残存水分とキシレンを減圧留去して、マレイミド樹
脂を得た。[Synthesis Example of Maleimide Resin] Synthetic Examples 1 to 5 Maleic anhydride was melted in accordance with the composition shown in Table 1, and aromatic diamine was gradually added thereto.
A dehydration reaction was carried out under the reduced pressure of 00 mmHg under the conditions shown in Table 1. After the reaction, 20 g of xylene and 200 g of hot water were added,
The mixture was stirred and mixed under reflux for 5 minutes. When left stationary,
Extracted water separates into the upper layer. This was removed by suction, 200 g of hot water was further added twice, and the washing was repeated in the same manner. Then, residual water and xylene were distilled off under reduced pressure to obtain a maleimide resin.
実施例 １〜５ 合成例１〜４で得られたマレイミドを第２表の配合に従
って、粘度が５±３ポイズ（２５℃）になるよう、溶剤
で調整した。Examples 1 to 5 The maleimides obtained in Synthesis Examples 1 to 4 were adjusted with a solvent according to the formulation shown in Table 2 so that the viscosity was 5 ± 3 poise (25 ° C.).
表面処理を行ったガラスクロスに含浸させ、乾燥機中
で、１１０℃、５分間加熱して溶剤を除去し、プリプレ
ーズを作成した。揮発分は０．５％以下であり、溶剤は
ほとんど残存していなかった。The surface-treated glass cloth was impregnated and heated in a dryer at 110 ° C. for 5 minutes to remove the solvent, thereby preparing a pre-pray. The volatile content was 0.5% or less, and almost no solvent remained.
上記プリプレーグを８枚重ね、加熱加圧して積層板を得
た。Eight of the above prepregs were stacked and heated and pressed to obtain a laminated plate.
比較例１〜５ N −メチルピロリドン（ＮＭＰ）を溶剤として、合成例
５で得られた樹脂組成物及びビスマレイミド（ＢＭ
Ｉ）、ケルイミド（ＫＩ）を第２表の配合に従い、配合
粘度が５±３ポイズ（２５℃）になるよう、溶剤で調整
した。但し、比較例２は不溶物が多量に残って、ワニス
化ができなかった。Comparative Examples 1 to 5 Using the N-methylpyrrolidone (NMP) as a solvent, the resin composition and the bismaleimide (BM) obtained in Synthesis Example 5 were used.
I) and kelimide (KI) were adjusted with a solvent according to the formulation of Table 2 so that the compounding viscosity was 5 ± 3 poise (25 ° C.). However, in Comparative Example 2, a large amount of insoluble matter remained and varnishing was not possible.
比較例１と比較例３〜５は表面処理を行ったガラスクロ
スに含浸させ、乾燥機中で加熱して、溶剤を除去し、プ
リプレーグを作成した。揮発分は、実施例１〜５に比べ
多い。In Comparative Example 1 and Comparative Examples 3 to 5, surface-treated glass cloth was impregnated and heated in a drier to remove the solvent to prepare prepregs. The volatile content is higher than in Examples 1-5.
更に、各々プリプレーグを８枚重ね、加熱加圧して積層
板を得た。Further, eight prepregs were stacked and heated and pressed to obtain a laminated plate.
ＤＳＣは、溶剤を添加しない配合物について測定した。
実施例１〜５は、比較例１〜５に比べ、発熱ピーク温度
が２０℃以上低く、硬化性の良いことがわかる。DSC was measured on the formulation without the addition of solvent.
As compared with Comparative Examples 1 to 5, Examples 1 to 5 have lower exothermic peak temperatures of 20 ° C. or more, and it is understood that the curability is good.
積層板の層間剥離強度、寸法安定性、ドリル加工性は良
好であり、後硬化なしで高いガラス転移温度が得られ
た。The laminate had good delamination strength, dimensional stability, and drillability, and a high glass transition temperature was obtained without post-curing.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−34895（ＪＰ，Ａ) 特開 昭53−82899（ＪＰ，Ａ) 特開 昭56−104924（ＪＰ，Ａ) 特公 昭60−17450（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-53-34895 (JP, A) JP-A-53-82899 (JP, A) JP-A-56-104924 (JP, A) JP-B-60- 17450 (JP, B2)
Claims (2)
から得られるビスマレイミドを４０〜７０重量％及び分
子量５００〜５０００のプレポリマーを６０〜３０重量
％含有するマレイミド樹脂(A)、エポキシ樹脂(B)、及び
フェノール樹脂(C)を必須成分とし、該組成比が(B)／
(A)が０．１〜２であり、(C)／(A)が０．０５〜０．５
である組成物を溶剤に溶かしてなる変性マレイミド樹脂
ワニス。1. A maleimide resin (A) and an epoxy resin containing 40 to 70% by weight of a bismaleimide obtained by the reaction of maleic anhydride and an aromatic diamine and 60 to 30% by weight of a prepolymer having a molecular weight of 500 to 5000. (B) and phenol resin (C) as essential components, and the composition ratio is (B) /
(A) is 0.1 to 2, (C) / (A) is 0.05 to 0.5
A modified maleimide resin varnish obtained by dissolving the above composition in a solvent.
囲第１項記載の変性マレイミド樹脂ワニス。2. The modified maleimide resin varnish according to claim 1, wherein the solvent is a cyclic ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62182264A JPH0613672B2 (en) | 1987-07-23 | 1987-07-23 | Modified maleimide resin varnish |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62182264A JPH0613672B2 (en) | 1987-07-23 | 1987-07-23 | Modified maleimide resin varnish |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6426681A JPS6426681A (en) | 1989-01-27 |
| JPH0613672B2 true JPH0613672B2 (en) | 1994-02-23 |
Family
ID=16115214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62182264A Expired - Lifetime JPH0613672B2 (en) | 1987-07-23 | 1987-07-23 | Modified maleimide resin varnish |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613672B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835543B2 (en) * | 1976-12-28 | 1983-08-03 | 三菱電機株式会社 | Heat resistant resin composition |
| JPS56104924A (en) * | 1980-01-25 | 1981-08-21 | Hitachi Ltd | Thermosetting resin composition |
-
1987
- 1987-07-23 JP JP62182264A patent/JPH0613672B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6426681A (en) | 1989-01-27 |
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